Synthesis of 3-acetyl-2-amino-4-pyridone

A method hxsynthesizing 3-acetyl-2-amino-4-pyyridone has been suggested. The synthesis involves the condensation of dimethylformamide dimethylacetal at the NH₂ group of diphenylboron chelate diacetylketene aminal followed by its intramolecular cyclization under the action of NaOMe in MeOH.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179. January, 1996.     

Various approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile in heterocyclic synthesis

Two approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile (1) in heterocyclic synthesis are considered. A method for preparing 3-acetyl-4-amino-5-cyano-2-methylpyridine directly from1 andN,N-dimethylformamide dimethylacetal (DMF DMA) was proposed, together with a synthetic route to 2-(2-amino-3-cyano-6-hydroxy-phenyl)-8-cyano-5-hydroxy-4-methylquinoline based on the transformation of hydroxyvinyl ketone1 into its diphenylboron chelate and condensation of the latter with DMF DMA. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 127–130, January, 1997.     

Synthesis and X-ray study of a bis-diphenylboron chelate of 3-(diaminomethylene)pentane-2,4-dione

A bis-diphenylboron chelate has been synthesized from 3-(diaminomethylene)pentane-2,4-dione through the action of (butylthio)diphenylborane and its molecular and crystal structures have been determined. The two boron -containing rings have the same six-membered skeleton but differ substantially in conformation and geometric parameters.Translated fromlzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2733–2735, November, 1996,     

Synthesis of 4-acetyl-5(3)-amino-3(5)-methylpyrazoles and pyrazolo[3,4-d]pyrimidines from diacetylketeneN,S-acetal

Isomeric 4-acetyl-5-amino-3-methyl- and 4-acetyl-3-amino-5-methylpyrazoles (2, 3) were formed in the reaction of hydrazines with 3-[amino(methylthio)methylene]pentan-2,4-dione (1) (diacetylketeneN,S-acetal). Pyrazolo[3,4-d]pyrimidines (5a,b) were synthesized by condensation of 4-acetyl-5-amino-1,3-dimethylpyrazole (2a) with amide dimethylacetals followed by treatment with ammonium acetate. The structures of the compounds obtained were confirmed by¹³C and¹⁵N NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1429–1433, August, 1993.     

3-Cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines in the synthesis of substituted 3-(aminomethyl)pyridines

The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.     

3-Acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile:E,Z-isomerism and the ability to form chelates

The Ni acetylacetonate-catalyzed addition of acetylacetone to malononitrile was shown to afford 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile. The diphenyl boron chelate of the latter with a -diketone-type structure was obtained.E,Z-isomerism of the chelate and the free ligand were investigated. TheZ-isomers were found to dominate in low polarity solvents.The work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08964).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1432–1435, August, 1994.     

Chelate synthesis of pyrazolyl(ethoxycarbonyl)ketene aminals,the precursors of functionalized pyrazolo[1,5-c]pyrimidines

A scheme for the preparation of novel synthetic reagents. pyrazolyl(ethoxycarbonyl)ketene aminals, from acetyl(ethoxycarbonyl)ketene (N-benzoyl)aminalvia its difluoroboron chelate is suggested. The possibility of cyclization of the ketene aminals obtained into functionally substituted pyrazolo[1,5-c]pyrimidines is shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2211–2214, December, 1994.This work was carried out with the support of the International Science Foundation (ISF, Grant No. M5Q 000), and a part of the work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08964).     

Chelate synthesis of 3-ethoxycarbonyl-4-hydroxy-2-trifluoromethylpyridine from ethyl acetoacetate and trifluoroacetonitrile

Ethyl 2-acetyl-3-amino-4,4,4-trifluoro-2-butenoate was synthesized by treatment of ethyl acetoacetate with CF₃CN in the presence of Ni(acac)₂. Condensation of the diphenylboron chelate of the former with dimethylformamide dimethylacetal followed by refluxing in ethanol yielded 3-ethoxycarbonyl-4-hydroxy-2-trifluoromethylpyridine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1329–1331, July, 1995.This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-08964).     

Functionalized sulfur-containing compounds. 13. Synthesis of substituted 3-amino-2-(organylsulfinyl)-and-(organylsulfonyl)thieno[2,3-b]pyridines

A method for the synthesis of substituted 3-amino-2-(organylsulfinyl)thieno[2,3-b]pyridines by the Thorpe—Ziegler intramolecular cyclization of substituted 3-cyano-2-[(organyl-sulfinyl)methylthio]pyridines was proposed. 3-Amino-2-(organylsulfonyl)thieno[2,3-b]pyridines were obtained by reactions of substituted 3-cyanopyridine-2-thiones with chloromethyl organyl sulfones. The reaction intermediates 3-cyano-2-[(organylsulfonyl)methylthio]pyridines were transformed into 3-amino-2-(organylsulfonyl)thieno[2,3-b]pyridines. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 510–515, March, 2006.     

Preparative synthesis of 3-cyano-4-difluoromethyl- and 3-cyano-4-trifluoromethyl-2(1H)-pyridones

An efficient procedure for the synthesis of 3-cyano-4-difluoromethyl- and 3-cyano-4-trifluoromethyl-2(1H)-pyridones was developed. The structure of one of the resulting compounds was established by X-ray diffraction analysis.     

One-step synthesis of 5-acetyl-2-amino-4-aryl-3-cyano-4H-pyrano[3,2-b]indoles. Molecular and crystal structure of 5-acetyl-2-amino-4-(4"-chloro-3"-nitrophenyl)-3-cyano-4H-pyrano[3,2-b]indole

A one-step procedure was developed for the synthesis of 5-acetyl-2-amino-4-aryl-3-cyano-4H-pyrano[3,2-b]indoles involving the three-component reaction of 1-acetylindol-3(2H)-one with aromatic aldehydes and malononitrile in ethanol in the presence of triethylamine as the catalyst. The structure of 5-acetyl-2-amino-4-(4"-chloro-3"-nitrophenyl)-3-cyano-4H-pyrano[3,2-b]indole was established by X-ray diffraction analysis.     

Cyclization of dialkyl(4-hydroxy-2-butynyl)-(3 isopropenylpropargyl)ammonium salts and intramolecular recyclization of the resultant products

2,2-Dialkyl(4-hydroxy-2-butynyl)(3-isopropenylpropargyl)ammonium chlorides in the presence of 0.2 molar equivalents of KOH in water undergo facile cyclization to give 2,2-dialkyl-4-hydroxymethyl-6-methylisoindolinium chlorides, which recyclize to dialkyl(6-methyl-1,3-dihydro-4-isobenzofuranylmethyl)amines by the action of a two-fold molar excess of KOH in water. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 528–532, April, 2007.     

Synthesis and Properties of Substituted Isoxazolo[3',4':4,5]thieno[2,3-b]pyridines

We synthesized derivatives of a novel heterocyclic system, isoxazolo[3',4':4,5]thieno[2,3-b]pyridine by sequential conversions in three steps: isomerization of 2-(2-R-ethylthio-2-oxo)-3-pyridyl cyanides obtained by alkylation from substituted 3-cyano-2(1H)-pyridinethiones by -halomethyl ketones in alkaline medium, to form 3-aminothieno[2,3-b]pyridines; diazotization of the amino group followed by nucleophilic substitution of the diazonium group by an azido group, bypassing the step of isolating the diazonium salts; and thermolysis of the azides formed.     

(3aS,6aR)-1,3-二苄基-六氢-1H-噻吩并[3,4-d]咪唑-2,4-二酮制备方法的改进

( )-生物素,又称维生素H或辅酶R,化学名(3aS,4S,6aR)-六氢-2-氧-噻吩并[3,4-d]咪唑-4-戊酸,属于水溶性B族维生素,是整个生物界所必须的。生物素在维持动物正常发育,繁殖及保持皮肤、羽毛和骨骼健康中发挥重要作用。自1949年瑞士Roche公司首次开发化学全合成d-生物素后,经过几十     

(Z)-2-羟基-3-苯甲酰丙烯酸甲酯的合成及晶体结构

标题化合物C11H10O4的晶体结构用X-射线单晶衍射法测定。晶体属单斜晶系, P21/c空间群, 晶胞参数a = 12.136(1), b = 5.559(1), c = 14.615(2) ? b = 96.758(3), V = 979.1(3) ?, Z = 4, Mr = 206.19, Dc = 1.399 g/cm3, F(000) = 432, m(MoKa) = 0.107 mm-1。晶体结构用直接法解出, 经全矩阵最小二乘法对原子参数进行修正, 最终的偏离因子为R = 0.0453, wR = 0.0990。标题化合物形成了1个大的共轭体系, 含有1个稳定的烯醇结构。结构测定表明还存在着1个分子内氢键的结构, 它使烯醇结构更加稳定。     

5-Acetyl-6-amino-4-methylthio-2-phenylpyrimidine and its use in the synthesis of functionalized pyrido[2,3-d]pyrimidines and pyrimido-[4,5-d]pyrimidines

Schemes for the synthesis of MeS-substituted pyrido[2,3-d]pyrimidin-5-one, pyrimido[4,5-d]pyrimidine, and 4-methylenepyrimido[4,5-d]pyrimidin-2-one based on 5-acetyl-6-amino-4-methylthio-2-phenylpyrimidine, which was prepared from the adduct of benzoyl isothiocyanate with acetylketeneN-benzoylaminal, were suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1324–1328, July, 1995.The work was carried out with financial support from the Russian Foundation for Basic Research (Grant No. 94-03-08964).     

Synthesis and Stereochemistry of (1S,3S,4S,7R11R)-3-(4-Nitrophenyl)-11-aza-2,6-dioxatricyclo[5,3,1,04,11]undecane

The reaction of (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol with glutaraldehyde has been studied. It has been established on the basis of AM1 and PM3 calculations and ¹H NMR spectra recorded in the presence of the shift reagent Eu(fod)₃ that (1S,3S,4S,7R,11R)-3-(4-nitrophenyl)-11-aza-2,6-dioxatricyclo[5,3,1,0^4,11]undecane is formed as the result of the reaction.     

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

Three new approaches to the synthesis of 1-bromo-3S-methylundecane, a key synthon in the synthesis of (S,S,S)-diprionylacetate, a sex pheromone of pine sawflies of the genera Diprion and Neodiprion, were proposed based on chemo-and stereoselective transformations of L-(-)-menthol derivatives. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 73–76, January–February, 2006.     

N-3-Oxoalkylamides and -Thioamides in the Synthesis of Heterocyclic Compounds. 7. Study of the Cyclization of N-(3-Oxoalkyl)amides of Tosylacetic Acid

Alkyl-substituted N-(3-oxoalkyl)amides of tosylacetic acid are cyclized under the action of bases with the formation of 3-tosyl-3,6-dihydropyridin-2(1H)-ones. In the presence of a phenyl substituent at position C₍₁₎ of the 3-oxoalkyl chain the reaction proceeds with the formation of 2-pyridones. The principles influencing the regiodirection of cyclization are explained.     

2-氰基-3-(4-甲基苯并[d]噻唑-2-氨基)-3-苯基丙烯酸酯类化合物的合成及抗病毒活性

以氰乙酸乙酯(氰乙酸)为起始原料,经酯化、缩合、氯化,然后与2-氨基-4-甲基苯并[d]噻唑反应,合成了20个新化合物4.所有化合物结构经过IR,1H NMR,13C NMR和元素分析确证.初步生物活性测试表明:在500μg·mL-1浓度下,该类化合物4具有一定的抗黄瓜花叶病毒(CMV)及抗烟草花叶病毒(TMV)室内活体治疗活性,其中化合物4b,4o,4q对CMV具有较好的活体治疗活性(抑制率分别为45.81%,43.20%,43.09%),化合物4d,4f,4h,4l对TMV具有较好的活体治疗活性(抑制率分别为45.68%,45.19%,45.86%,44.32%),对照药宁南霉素的活体治疗活性分别为56.31%,54.63%.